Hard–soft–hard triblock copolymers based on poly­(ethylene oxide) (PEO), poly­(2-naphthyl glycidyl ether)-block-poly­[2-(2-(2-methoxy­ethoxy)­ethoxy)­ethyl glycidyl ether]-block-poly­(2-naphthyl glycidyl ether)­s (PNG-PTG-PNGs), were synthesized by sequential ring-opening polymerization of 2-(2-(2-methoxy­ethoxy)­ethoxy)­ethyl glycidyl ether and 2-naphthyl glycidyl ether using a bidirectional initiator catalyzed by a phosphazene base. Four PNG-PTG-PNGs had different block compositions (f wt,PNG = 9.2–28.6 wt %), controlled molecular weights (M n = 23.9–30.9 kDa), and narrow dispersities (Đ = 1.11–1.14). Most of the PNG-PTG-PNG electrolytes had much higher Li+ conductivities than that of a PEO electrolyte (6.54 × 10–7 S cm–1) at room temperature. Eespecially, the Li+ conductivity of PNG18-PTG107-PNG18 electrolyte (9.5 × 10–5 S cm–1 for f wt,PNG = 28.6 wt %) was comparable to one of a PTG electrolyte (1.11 × 10–4 S cm–1). The Li+ conductivities of PNG-PTG-PNG electrolytes were closely correlated to efficient Li+ transport channels formed by the microphase separation into soft PTG and hard PNG domains.

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